Malonates and derivatives for in-situ films

ABSTRACT

The present teachings contemplate a method comprising coating an polymeric material with a composition including a dicarbonyl compound and having a viscosity of from about 50 cps to about 500 cps, wherein the coating initiates either: (i) spontaneous polymerization (e.g., in less than about one minute) at room temperature of the composition without the addition of an initiator; or (ii) polymerization at room temperature at a selected later time with or without the addition of an initiator; and wherein the composition adheres or facilitates adhesion of the polymeric material to a substrate.

TECHNICAL FIELD

The present invention relates generally to malonate coatings, films orsimilar treatments that allow for easily controlled polymerization.

BACKGROUND

In the transportation and construction industries, among others,polymeric adhesives, sealants and foams are frequently used to providestructural support, sealing, and sound attenuation. Coatings, handlingfilms, or the like (referred to herein generally as coatings) arefrequently utilized in conjunction with such materials. However, manysuch coatings or even the adhesives, sealants or foams themselvespresent significant challenges in adhering to certain substrates,especially substrates that may be coated with contaminates such as oil.Furthermore, many existing coatings require the addition of aninitiating substance or environment in order to polymerize and adhereduring application to a substrate

U.S. Pat. Nos. 8,609,885; 8,884,051; and 9,181,365 and U.S. PublicationNos. 2014/0329980 and 2015/0056879 may be relevant to the presentteachings, and are all incorporated by reference for all purposes.

Notwithstanding the above teachings, there has remained a need forcoatings that are capable of polymerization at room temperature uponcontact with certain substrates without need for any initiator. There isa further need for coatings that are capable of adhering to substratesthat typically present challenges in adhesion, especially contaminatedsubstrates.

SUMMARY OF THE INVENTION

One or more of the above needs are met by the present teachings whichcontemplate a method comprising coating a material with a compositionincluding a dicarbonyl compound represented by the formula

the composition having a viscosity of from about 50 cps to about 500cps, wherein the coating process initiates either: (i) spontaneouspolymerization (e.g., in less than about one minute) at room temperatureof the composition without the addition of an initiator; or (ii)polymerization at room temperature at a selected later time with orwithout the addition of an initiator; and wherein the compositionassists in adhering the coated material to a substrate (e.g., bypermitting penetration of the material through the coating to thesubstrate).

The material which receives the coating may be a polymeric material. Thematerial may be an expandable material. The substrate to which thecoated material is adhered may be a metallic material. The substrate maybe a contaminated substrate (e.g., coated in oil or the like). Thesubstrate may be a polycarbonate material. One or more of the substrateand material may be nucleophilic. The substrate and/or material may havea pH of greater than 7. The coating step may comprise applying thecomposition to the material as a film. The coating step may includespray coating, roll coating, brushing, dipping or any combinationthereof. The composition may form a handling film. Polymerization of thecomposition may occur at least 5 minutes, at least 15 minutes or even atleast 30 minutes after coating. Polymerization of the composition mayoccur less than 1 hour, less than 30 minutes, less than 15 minutes, oreven less than 5 minutes after coating. The substrate may be a sheetmolding compound (SMC) material. The composition may be stored in acontainer comprising one or more materials having a neutral pH (e.g., apH of less than 7). The composition may be formed as a paste. Thecomposition may include a colorant. One or more of the material and/orsubstrate may be formed with a bisphenol A precursor. The method mayinclude welding the material after coating. The coated material may be atape. The tape may include a first surface containing a pressuresensitive adhesive. The tape may include a surface that is a heatactivated adhesive. The coated material may form a laminate when appliedto the substrate. The composition may be formed for locating into a gluegun application device. The composition may be stored in a polyethylenecontainer. The substrate may be concrete. The substrate may be coatedwith an oil-based substance. The oil-based substance may be 61 MALHCL 1. The coating may form a tack-free surface on the material. Themethod may include heating the coated material on the substrate to causeadhesion of the composition and/or material to the substrate. Thematerial may be a tacky material. The material may be a tack-freematerial. The material may be an epoxy-containing material. The materialmay include an ethylene copolymer. The composition may include one ormore of a diethyl (e.g., diethyl methylmalonate), dimethyl, hexylmethyl, ethyl ethoxy ethyl, ethyl cyclohexyl, 2-phenylpropyl ethyl,dicyclohexyl, and fenchyl methyl.

The material may be a structural adhesive. The composition may increasedimensional stability of the adhesive. A reinforcing layer may be addedto the material and composition so that the reinforcing layer is: (i)located on the surface of the material; (ii) located within (e.g.,substantially surrounded by) the material; (iii) formed as a bead ofextruded material; or (iv) any combination thereof. A reinforcing layermay be added to the material and composition and the reinforcing layermay comprise a scrim, a yarn, a fiber, a bead of solid epoxy-containingmaterial, a weave, fibers (e.g., glass, carbon, Kevlar or the like), amesh, or any combination thereof. One or more of the material orcomposition may include a thermoplastic epoxy component. A reinforcinglayer may be added to the material and composition and the reinforcinglayer may be a recyclable material. The material may be selected from asealant, and adhesive, a patch, a tape, or any combination thereof. Thecomposition and material may be reprocessed (e.g., recyclable) withoutproperty degradation of the material. The material may penetrate thecomposition and adhere to the underlying substrate. The coating mayimprove the handling of the material. The coating may improve theadhesion of the underlying material. The coating may improve theweldability of the material. The weldability may be improved by thecomposition modifying one or more physical characteristics of thematerial to which it is applied. The weldability may be improved bymodifying the one or more of the rheology and/or surface characteristicsof the material by use of the coating.

The teachings herein further provide for a structure comprising apolymeric material, a composition including a dicarbonyl compoundrepresented by the formula

coated located onto the polymeric material and a substrate having a pHof greater than 7 located in contact with the composition.

The teachings herein also provide for a method comprising coating npolymeric material with a composition including a dicarbonyl compoundrepresented by the formula

and having a viscosity of from about 50 cps to about 500 cps, whereinthe coating polymerizes upon the addition of an initiator and whereinthe composition adheres the polymeric material to a substrate and/or thepolymeric material penetrates the composition to adhere to thesubstrate.

The present teachings further contemplate a device comprising anexpandable material, an open mesh weave located in planar contact withthe expandable material and along the entirety of the expandablematerial, and a malonate handling film applied to at least a portion ofopen mesh/expandable material assembly. The expandable material may betacky prior to expansion allowing the expandable material to adhere tothe open mesh weave. It also may allow, prior to expansion, adhesion toa surface for reinforcing the surface, at least in desired areas, butwith allowing efficiently and effectively handling from themanufacturing line of the device, to the installation in the vehicle.

The device may be configured to conform to the shape of the surface. Thedevice may be flexible (e.g., capable of easily bending withoutbreaking) prior to expansion of the expandable material. The device maybend under its own weight when held at its end. The volumetricactivation of the activatable material may be at least about 100% andless than about 300%. The expandable material may include a structuraladhesive material. The expandable material may include a sealantmaterial.

The present teachings further contemplate a method for structurallyreinforcing a vehicle body stamping comprising forming a tackyexpandable structural adhesive material and locating an open meshmaterial onto the expandable material. The method may further includeapplying a handling coating to all or part of the open mesh/expandablematerial assembly. The coating may comprise a malonate composition whichmay be a malonate film. The method may further include contacting theopen mesh and expandable material with a vehicle body stamping surfaceand activating the expandable material to expand by application of heat.The open mesh and expandable material may remain in contact with thestamping surface by means of the tacky nature of the expandable materialin a portion not covered by the handling coating or via anotherattachment method, prior to activating the expandable material.

The method may be free of any separate fastening step for connecting thereinforcement member to the body stamping. The method may include aseparate fastening step for connecting the reinforcement member to thebody stamping. The method may include flexing the expandable materialand mesh to conform to the shape of the body stamping prior toactivating the expandable material. The method may include cutting theexpandable material to a desired shape prior to locating the mesh ontothe expandable material. The method may include cutting the expandablematerial and mesh located thereon to a desired shape prior to contactingthe mesh and expandable material with the vehicle body stamping surface.The step of forming the tacky expandable structural adhesive materialmay be free of any molding process. The step of locating the mesh ontothe expandable material may be free of any separate fastening step forconnecting the mesh to the expandable material. The step of activatingthe expandable material includes volumetric expansion of at least about100% and less than about 300%. The method may include flexing theexpandable material and mesh so that a first portion of the mesh andexpandable material is arranged at an angle of 90° or less from a secondportion of the mesh and expandable material. The method may includeflexing the expandable material and mesh so that a surface of thevehicle body stamping is contacted by the mesh and expandable materialthat would not be contacted by the mesh and expandable material if themesh and expandable material were substantially rigid. The mesh may belocated onto the expandable material so that the expandable materialsubstantially covers the mesh and is free of any voids on the mesh thatare not covered with the expandable material prior to activation. Theopen mesh and expandable material may no longer be flexible afteractivation of the expandable material. The open mesh and expandablematerial may continue to be flexible after activation of the expandablematerial.

DETAILED DESCRIPTION

The explanations and illustrations presented herein are intended toacquaint others skilled in the art with the invention, its principles,and its practical application. Those skilled in the art may adapt andapply the invention in its numerous forms, as may be best suited to therequirements of a particular use. Accordingly, the specific embodimentsof the present invention as set forth are not intended as beingexhaustive or limiting of the teachings. The scope of the teachingsshould, therefore, be determined not with reference to the abovedescription, but should instead be determined with reference to theappended claims, along with the full scope of equivalents to which suchclaims are entitled. The disclosures of all articles and references,including patent applications and publications, are incorporated byreference for all purposes. Other combinations are also possible as willbe gleaned from the following claims, which are also hereby incorporatedby reference into this written description.

This application is related to and claims the benefit of the prioritydate of U.S. Provisional Application Ser. Nos. 62/325,818, filed on Apr.21, 2016; 62/396,435, filed on Sep. 19, 2016; and 62/395,012, filed onSep. 15, 2016. The entirety of these applications are herebyincorporated by reference for all purposes.

The present teachings contemplate the use of a malonate-basedcomposition (e.g., a monomeric composition) for coating (e.g., applyingas film to) a secondary material (which may be a polymeric material).Any reference herein to the material to which the coating is applied maybe referring to the material in its unactivated (e.g. uncured or green)state or in its activated (e.g., cured) state. The composition maypreferably comprise a diethyl malonate (DEM). The composition maycomprise a dimethyl malonate (DMM). The composition may preferablycomprise a diethyl methylmalonate (DEMM). The composition may includeone or more additional components which may be selected from adhesionpromoters and initiators. The composition may include a cyanoacrylate(e.g., methyl 2-cyanoacrylate, ethyl-2-cyanoacrylate,n-butylcyanoacrylate and 2-octylcyanoacrylate). The composition mayinclude one or more of a diethyl, dimethyl, hexyl methyl, ethyl ethoxyethyl, ethyl cyclohexyl, 2-phenylpropyl ethyl, dicyclohexyl, and fenchylmethyl.

The malonate composition may be a one part material that polymerizeseither immediately or at some later designated time at room temperature(e.g., at a temperature of from about 20° C. to about 25° C.). It isalso possible that some heat may be utilized for polymerization. It isquite possible that the malonate composition polymerizes at roomtemperature without the addition of any initiator or stimulus. However,it is also possible that an initiator or stimulus may be utilized tocause polymerization of the composition. Suitable stimuli includes butare not limited to ultra-violet light. The composition may be such thatthe time of polymerization can be modified so that it is “on demand”. Inother words, the composition can be applied as a coating (e.g. as afilm) to a secondary material to provide sufficient open time forapplication of the coating with no polymerization such that thecomposition does not polymerize until contact with a substrate ofchoice. Thus, open time for the application process can extend a numberof minutes or even an hour without fear of early polymerization. It ispossible that only contact with certain substrates initiatespolymerization of the composition.

The teachings herein are also directed to a method whereby a materialthat has one or more characteristics that make it difficult to handle(e.g., that the material is tacky, that it is subject to sag, that theviscosity is lower than desired, that the surface energy is lower thandesired) is coated with a composition to assist in ameliorating one ormore of these characteristics. The surface of the material that receivesthe coating may then be located onto a substrate. The substrate may be amaterial that is typically difficult to adhere to, whether by thephysical characteristics of the substrate itself, or the presence of atreatment (e.g., oil) that presents challenges for adhering. Theproperties of the substrate may be selected such that upon contact withthe material the composition polymerizes. However, it is also possiblethat the composition polymerizes upon contact with the substrate. It ispossible that the composition remains as a layer between the materialand the substrate. It is possible that the composition improves adhesionbetween the material and the substrate. It is possible that the materialpermeates the composition coating to adhere directly to the substrate.It is possible that only the composition adheres to the substrate. Thematerial may be an activatable material such that upon coating thematerial with the composition, the material is in its unactivated or“green” state. Thus, despite the fact that the material adheressufficiently upon activation, the composition may assist in adhering thematerial to the substrate prior to activation.

At some later time, after applying the coated material to a substrate,the material may be activated by the addition of a stimulus. Thestimulus may be a physical stimulus or chemical stimulus. The materialmay be activated by the addition of heat. Upon activation, the materialmay expand and/or otherwise cure forming a more rigid material that isgenerally dry to the touch, but may possibly remain tacky.

The coating may provide one or more of the following benefits. Thecoating may form a tack-free surface on an otherwise tacky material. Thecoating may adhere the secondary material to a substrate. The coatingmay be such that the secondary material may permeate the coating so thatthe secondary material adheres to the substrate. The coating may undergopolymerization at room temperature with no additional initiator orstimulus. The coating may allow for de-bonding of the secondary materialfrom a substrate. The coating may provide sufficient adhesion of thesecondary material to substrates which are generally difficult to adhereto. The coating may provide sufficient adhesion to contaminated surfacessuch as those coated in oil-based substances. The coating may improvethe weldability of a material to which the coating is applied. Thecoating may improve tack and/or adhesion. The coating may allow for theaddition of a color or other appearance attribute. The coating mayimprove the energy absorption of a material to which the coating isapplied. The coating may improve the reflectivity of a surface to whichit is applied. The coating may improve the tactile safety of a surfaceto which the coating is applied. The coating may assist in minimizingabrasion of the material. The coating may act to absorb one or morecontaminants present on one or more of the material, the substrate orboth. The coating may be a formulation that facilitates simplifiedreprocessing. For example, the underlying material may be easilyrecycled or reprocessed with the coating still located thereon withminimal or no degradation to the material.

As mentioned, the composition may be applied to a secondary polymericmaterial. Immediate polymerization at room temperature may occur whenthe coated polymeric material is applied to the secondary material.Polymerization may occur only upon contact of the composition with asubstrate (after application of the composition to the secondarymaterial). It is also possible that that the composition may polymerizevia electropolymerization, mechanically initiated polymerization, dualcure polymerization, thermally initiated polymerization, coordinationpolymerization, or nucleophilic polymerization. The composition mayundergo solution or emulsion polymerization. It is also possible thatthe composition undergoes random copolymerization or blockcopolymerization. The composition may undergo anionic polymerization.The composition may undergo free radical polymerization.

When selecting the composition to utilize as a coating for a polymericmaterial, one or more of glass transition temperature (T_(g)),flexibility, reactivity, toughness, adhesion capability, rigidity, speedof reactivity or heat resistance may provide motivation for suchselection. The coating may preferably be a malonate material. As anon-limiting example, a diethyl material may provide rapid reactivity. Adimethyl material may provide high reactivity. A hexyl methyl materialmay provide flexibility and toughness. An ethyl ethoxy ethyl materialmay provide improved adhesion and flexibility. An ethyl cyclohexylmaterial may provide rigidity, stiffness and rapid reactivity. A2-phenylpropyl ethyl material may provide stiffness and improvedadhesion. A dicyclohexyl material may provide a high T_(g), stiffnessand heat resistance. A fenchyl methyl material may provide high T_(g),high rigidity, slow reactivity and heat resistance. Accordingly,depending on the intended use of the secondary polymeric material andthe intended substrate upon which the polymeric material may be located,it is possible to select a coating which provides attributes which willbenefit the intended use.

Polymeric materials coated with the compositions taught herein may haveimproved properties as compared to the polymeric materials with nocoating. The coated polymeric materials may have improved mechanicalproperties such as increased tensile strength, improved modulus,improved hardness, increase impact strength, increased UV stability andimproved crystallinity. The coated polymeric materials may have improvedbarrier capabilities against oxygen, carbon dioxide, water and othersubstances. The coated polymeric materials may have improved rheology,ductility and elasticity. The coated polymeric materials may haveimproved thermal characteristics and higher heat distortiontemperatures. The coated polymeric materials may have improvedelectrical properties, improved optical properties, and improvedthermodynamic properties. The coating may modify the surface energy ofthe polymeric material and improve wetting and adhesion. Thethermodynamic nature and surface energy characteristics of the coatingcompositions may account for the ability of the compositions to adhereto oily substrates.

It is possible that contact between the coating composition and certainsubstrates may cause polymerization of the coating compositions. Certainbasic substrates (e.g., those having a pH of greater than 7) may causepolymerization (and thus possibly adhesion) of the coating composition,which may thus adhere the secondary polymeric material to the substrate.It is also possible that acidic substrates (e.g., those having a pH ofless than 7) may not cause polymerization of the coating composition.However, the coating may be utilized in systems having materials and/orsubstrates with pH of lower than 7, but an initiator may be required forthe coating to polymerize. It is also possible that the more basic asubstrate (the higher the pH) the more quickly the coating compositionwill polymerize. Thus, acidic materials may be included in the system toslow polymerization if so desired. Nucleophilic substrates may alsoinitiate polymerization of the coating composition. It is possible thatincreased nucleophilicity will initiate polymerization more quickly.Some examples of substrates which act to initiate polymerization of thecoating compositions disclosed herein include polycarbonate, SMC,Kevlar, concrete or other basic substrates. Some examples of substrateswhere the coating compositions may not polymerize, thereby possiblyrequiring an initiator or stimulus, include polyethylene, polypropyleneand Teflon.

The coating compositions may be utilized in the formation of tapes(which may be pressure sensitive), or any material requiringdifferential tack. The coating compositions may be utilized to formweldable materials. The adhesion capability of the coating compositionsmay be modified by raising the molecular weight of the coatingcomposition. Adhesion may occur upon initiation but may also be delayedpost-initiation.

The material to which the coating is applied may be at least partiallytacky at room temperature (e.g., about 23° C.) and may also be tacky attemperatures between about 0° C. and about 80° C. Additionally, thematerial preferably exhibits reinforcement characteristics (e.g.,imparts rigidity, stiffness, strength or a combination thereof to amember) upon cure when located onto a substrate. It is also preferablefor the material to be heat activated to expand or otherwise activateand wet surfaces which the material contacts. After expansion oractivation, the material preferably cures, hardens and adheres to thesurfaces that it contacts. For application purposes, it is oftenpreferable that the material exhibit flexibility, particularly when thematerial is to be applied to a contoured surface of a vehicle body. Onceapplied, however, it is typically preferable for the material to beactivatable to soften, expand (e.g., foam), cure, harden or acombination thereof. For example, and without limitation, a typicalmaterial will include a polymeric material, such as an epoxy resin orethylene-based polymer which, when compounded with appropriateingredients (typically a blowing and curing agent), expands and cures ina reliable and predicable manner upon the application of heat or theoccurrence of a particular ambient condition. From a chemical standpointfor a thermally-activated material, the material may be initiallyprocessed as a flowable material before curing. Thereafter, the basematerial preferably cross-links upon curing, which makes the materialsubstantially incapable of further flow.

The material may be an epoxy-based material which may be aliphatic,cycloaliphatic, aromatic or the like. The epoxy may be supplied as asolid (e.g., as pellets, chunks, pieces or the like) or a liquid. Theepoxy may include an ethylene copolymer or terpolymer that may possessan alpha-olefin. As a copolymer or terpolymer, the polymer is composedof two or three different monomers, i.e., small molecules with highchemical reactivity that are capable of linking up with similarmolecules. One exemplary epoxy resin may be a phenolic resin, which maybe a novalac type or other type resin. Other preferred epoxy containingmaterials may include a bisphenol-A epichlorohydrin ether polymer, or abisphenol-A epoxy resin which may be modified with butadiene or anotherpolymeric additive. Examples of suitable epoxy-based materials, whichmay be used as in the base material are sold under the productdesignations L5020, L5010, L5224, L8000, L5001 and are commerciallyavailable from L&L Products, Romeo, Mich. According to preferredformulations, the base material can include up to about 50% by weightepoxy resins, more preferably, up to about 65% by weight epoxy resins,and even more preferably up to about 80% by weight epoxy resins.

A substantial portion of the materials in the material will typicallyhave molecular weights that are low enough to maintain adhesivecapability of the base material. For an elastomer-based or epoxy-basedbase material, it is preferable for at least about 5% by weight of theelastomer or epoxy materials to have a molecular weight less than about1000 and more preferably at least about 10% by weight of the elastomeror epoxy materials have a molecular weight less than about 1000. It isalso contemplated that, for maintaining adhesive capability, componentssuch as plasticizers or processing oils may be added to elastomer-basedor epoxy-based materials and particularly to a thermoplastic-basedmaterial.

As general guidance for the material which receives the coating, it ispreferable that at least 1% by weight of the components have a lowenough molecular weight to be a liquid at about 23° C. More preferably,at least 5% by weight of the components have a low enough molecularweight to be a liquid at about 23° C. Still more preferably, at least10% by weight of the components have a low enough molecular weight to bea liquid at about 23° C.

In most applications, it is undesirable for the underlying materialitself be reactive at room temperature or otherwise at the ambienttemperature in a manufacturing environment (e.g. up to about 40° C. orhigher). More typically, the material becomes reactive at higherprocessing temperatures, such as those encountered in an automobileassembly plant. In such and embodiment, the material may be foamed uponautomobile components at elevated temperatures or at higher appliedenergy levels, e.g., during painting preparation steps. Whiletemperatures encountered in an automobile assembly operation may be inthe range of about 148.89° C. to 204.44° C. (about 300° F. to 400° F.),body and paint shop applications are commonly about 93.33° C. (about200° F.) or slightly higher. If needed, blowing agent activators can beincorporated into the base material to cause expansion at differenttemperatures outside the above ranges. Generally, suitable materials orfoams for the material have a range of expansion ranging fromapproximately 0 to over 1000 percent.

Advantageously, the material of the present invention may be formed orotherwise processed in a variety of ways. For example, preferredmaterials can be processed by injection molding, extrusion, compressionmolding or with a robotically controlled extruder such as amini-applicator. This enables the formation and creation of part designsthat exceed the capability of most prior art materials.

In the event that the system described herein includes a reinforcingmaterial, it may be an open mesh reinforcing material. The open meshmaterial of the present invention is at least partially open or hasthrough-holes. It is contemplated that it may be advantageous to allow asignificant portion of the underlying material to flow through the openportion and adhere to the vehicle structure that is opposite the openmesh layer. In a preferred embodiment, the open portion is at leastabout 25 percent of the area of layer 14, more preferably at least about40 percent, and most preferably at least about 50 percent, but less thanabout 90 percent. It is contemplated that the amount of area of the openportion be as high as possible while allowing the complete assembly tomaintain its desired structural performance and physical properties.

The reinforcing material located onto the underlying material receivingthe coating may include non-conductive threads or wire (e.g., elongatedfilament, fibrous, or fabric material), which may be applied as a mat, acloth, a roving, a netting, a mesh, a scrim, or the like. In suchembodiments, the strengthening material may be composed, for example, ofwoven or unwoven fibers, filaments or the like of cotton, glass (e.g.,E-glass or S-glass), fiberglass, Mylar, nylon, polyester, carbon,aramid, plastics, polymers (e.g., thermoplastics such as polyamides(e.g., nylon), PET (e.g., Mylar), polycarbonate, polyethylene,polypropylene, polybutylene (e.g., polybutylene terephthalate),polystyrene, polyurethane, vinyl, or any combination thereof, or othermaterials. As used herein, “threads,” or “wire” connotes a singlefilament of material, a braided bundle of filaments, or an unbraidedbundle of filaments.

In other applications, it may appreciable that the reinforcing materialmay be bead-like particles, aggregates, hollow material (e.g., hollowparticle), or otherwise, or any combination thereof. In suchembodiments, the strengthening material may be composed, for example, ofparticles or the like of glass (e.g., E-glass or S-glass), fiberglass,nylon, polyester, carbon, aramid, plastics, polymers (e.g.,thermoplastics such as polyamides (e.g., nylon), polycarbonate,polyethylene, polypropylene, polybutylene (e.g., polybutyleneterephthalate), polystyrene, polyurethane, vinyl, or any combinationthereof), or other materials.

As used herein, unless otherwise stated, the teachings envision that anymember of a genus (list) may be excluded from the genus; and/or anymember of a Markush grouping may be excluded from the grouping.

Unless otherwise stated, any numerical values recited herein include allvalues from the lower value to the upper value in increments of one unitprovided that there is a separation of at least 2 units between anylower value and any higher value. As an example, if it is stated thatthe amount of a component, a property, or a value of a process variablesuch as, for example, temperature, pressure, time and the like is, forexample, from 1 to 90, preferably from 20 to 80, more preferably from 30to 70, it is intended that intermediate range values such as (forexample, 15 to 85, 22 to 68, 43 to 51, 30 to 32 etc.) are within theteachings of this specification. Likewise, individual intermediatevalues are also within the present teachings. For values which are lessthan one, one unit is considered to be 0.0001, 0.001, 0.01, or 0.1 asappropriate. These are only examples of what is specifically intendedand all possible combinations of numerical values between the lowestvalue and the highest value enumerated are to be considered to beexpressly stated in this application in a similar manner. As can beseen, the teaching of amounts expressed as “parts by weight” herein alsocontemplates the same ranges expressed in terms of percent by weight.Thus, an expression in the of a range in terms of “at least ‘x’ parts byweight of the resulting composition” also contemplates a teaching ofranges of same recited amount of “x” in percent by weight of theresulting composition.”

Unless otherwise stated, all ranges include both endpoints and allnumbers between the endpoints. The use of “about” or “approximately” inconnection with a range applies to both ends of the range. Thus, “about20 to 30” is intended to cover “about 20 to about 30”, inclusive of atleast the specified endpoints.

The disclosures of all articles and references, including patentapplications and publications, are incorporated by reference for allpurposes. The term “consisting essentially of to describe a combinationshall include the elements, ingredients, components or steps identified,and such other elements ingredients, components or steps that do notmaterially affect the basic and novel characteristics of thecombination. The use of the terms “comprising” or “including” todescribe combinations of elements, ingredients, components or stepsherein also contemplates embodiments that consist of, or consistessentially of the elements, ingredients, components or steps.

Plural elements, ingredients, components or steps can be provided by asingle integrated element, ingredient, component or step. Alternatively,a single integrated element, ingredient, component or step might bedivided into separate plural elements, ingredients, components or steps.The disclosure of “a” or “one” to describe an element, ingredient,component or step is not intended to foreclose additional elements,ingredients, components or steps.

It is understood that the above description is intended to beillustrative and not restrictive. Many embodiments as well as manyapplications besides the examples provided will be apparent to those ofskill in the art upon reading the above description. The scope of theinvention should, therefore, be determined not with reference to theabove description, but should instead be determined with reference tothe appended claims, along with the full scope of equivalents to whichsuch claims are entitled. The disclosures of all articles andreferences, including patent applications and publications, areincorporated by reference for all purposes. The omission in thefollowing claims of any aspect of subject matter that is disclosedherein is not a disclaimer of such subject matter, nor should it beregarded that the inventors did not consider such subject matter to bepart of the disclosed inventive subject matter.

What is claimed is:
 1. A method comprising coating an expandablepolymeric material with a composition including a dicarbonyl compoundrepresented by the formula

the composition having a viscosity of from about 50 cps to about 500 cpsas measured according to ASTM D1084, wherein the coating initiateseither: (i) spontaneous polymerization in less than about one minute atroom temperature of the composition without the addition of aninitiator; or (ii) polymerization at room temperature at a selectedlater time without the addition of an initiator; and wherein thecomposition adheres the expandable polymeric material to a substrate. 2.The method of claim 1, wherein the substrate is metallic.
 3. The methodof claim 1, wherein one or more of the expandable polymeric material andsubstrate are nucleophilic.
 4. The method of claim 1, wherein thesubstrate, the expandable polymeric material, or both have a pH ofgreater than
 7. 5. The method of claim 1, wherein the coating stepcomprises applying the composition as a film to the expandable polymericmaterial.
 6. The method of claim 1, wherein the coating step includesspray coating, roll coating, brushing, dipping or any combinationthereof.
 7. The method of claim 2, wherein the composition forms ahandling film.
 8. The method of claim 1, wherein polymerization of thecomposition occurs at least 5 minutes, at least 15 minutes or even atleast 30 minutes after coating.
 9. The method of claim 1, whereinpolymerization of the composition occurs less than 1 hour, less than 30minutes, less than 15 minutes, or even less than 5 minutes aftercoating.
 10. The method of claim 1, wherein the substrate is a sheetmolding compound (SMC) material. 11-12. (canceled)
 13. The method ofclaim 1, wherein the composition includes a colorant.
 14. The method ofclaim 1, wherein the expandable polymeric material is formed with abisphenol A precursor.
 15. The method of claim 14, including welding theexpandable polymeric material after coating.
 16. The method of claim 1,wherein the coated expandable polymeric material is a tape.
 17. Themethod of claim 15, wherein the tape includes a first surface containinga pressure sensitive adhesive formed by the coating and a second surfacethat is a heat activated expandable adhesive. 18-22. (canceled)
 23. Themethod of claim 2, wherein the substrate is coated with an oil-basedsubstance.
 24. (canceled)
 25. The method of claim 1, wherein the coatingforms a tack-free surface on the expandable polymeric material.
 26. Themethod of claim 1, including heating the coated expandable polymericmaterial on the substrate to cause adhesion of the composition to thesubstrate and/or expansion of the expandable polymeric material. 27-29.(canceled)
 30. The method of claim 1, wherein the polymeric materialincludes an epoxy component, an ethylene copolymer component, or both.31. The method of claim 30, wherein the composition includes one or moreof a diethyl, dimethyl, hexyl methyl, ethyl ethoxy ethyl, ethylcyclohexyl, 2-phenylpropyl ethyl, dicyclohexyl, and fenchyl methyl.32-91. (canceled)